Method of producing beta-sialon fluorescent material

ABSTRACT

Provided is a method of producing a β-sialon fluorescent material having a high light emission intensity and an excellent light emission luminance. The method includes preparing a calcined product having a composition of β-sialon containing an activating element; grinding the calcined product to obtain a ground product; and heat-treating the ground product to obtain a heat-treated product. A specific surface area of the ground product is 0.2 m 2 /g or more.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation application of U.S. patent application Ser. No.15/606,153, filed May 26, 2017, which claims the benefit of JapanesePatent Application No. 2016-107187 filed on May 30, 2016, and JapanesePatent Application No. 2017-97125 filed on May 16, 2017, the disclosuresof all which are hereby incorporated by reference in their entirety.

BACKGROUND Technical Field

The present disclosure relates to a method of producing a β-sialonfluorescent material.

Description of Related Art

Light emitting devices including, in combination, a light source and awavelength conversion member capable of emitting light with a huedifferent from the hue of the light source when excited by the lightfrom the light source, and thus capable of emitting light of varioushues owing to the principle of the mixture of colors of light, have beendeveloped. In particular, light emitting devices composed of a lightemitting diode (hereinafter referred to as “LED”) combined with afluorescent material are increasingly and widely utilized, for example,as lighting systems, backlights for liquid crystal display devices,small-sized strobes, and the like, and their spread is being advanced.For example, when a fluorescent material that emits light at shortwavelengths, such as blue-green, green, and yellow-green, is combinedwith a fluorescent material that emits light at long wavelengths, suchas orange and red, it is possible to improve color reproduction range ofliquid crystal display devices or color rendering properties of lightingsystems.

As such fluorescent materials, aluminate fluorescent materials, silicatefluorescent materials, sulfide fluorescent materials, phosphatefluorescent materials, borate fluorescent materials, and so on areknown. As a replacement of these fluorescent materials, fluorescentmaterials that have a nitrogen-containing inorganic crystal as a hostcrystal in a crystal structure, such as sialon fluorescent materials,oxynitride fluorescent materials, and nitride fluorescent materials,have been proposed as fluorescent materials exhibiting a small decreasein the luminance following a temperature increase and having excellentdurability.

Among these fluorescent materials, examples of a sialon fluorescentmaterial that is a solid solution of silicon nitride include an α-typesialon fluorescent material and a β-type sialon fluorescent material,which are different in a crystal structure from each other. The β-typesialon fluorescent material (hereinafter also referred to as “β-sialonfluorescent material”) is a highly efficient green fluorescent material,which is excited in a wide wavelength region of from near-ultravioletlight to blue light and has a peak light emission wavelength in therange of 520 nm or longer and 560 nm or shorter.

A β-sialon fluorescent material activated with europium (Eu) contains Euthat is an activating element, and a host crystal thereof is representedby a compositional formula: Si_(6-z)Al_(z)O_(z)N_(8-z) (0<z≤4.2). Theβ-sialon fluorescent material activated with Eu can be produced bymixing compounds serving as raw materials, for example, silicon nitride(Si₃N₄), aluminum nitride (AlN), and aluminum oxide (Al₂O₃), andeuropium oxide (Eu₂O₃) serving as an activation agent in a predeterminedmolar ratio and calcining the mixture at around 2,000° C.

Such fluorescent materials are desired to be enhanced in terms of alight emission luminance. In order to enhance the light emissionluminance, as a production method of the Eu-activated β-sialonfluorescent material, for example, Japanese Unexamined PatentPublication No. 2005-255895 discloses a method in which a calcinedproduct obtained through calcination of raw materials is furtherheat-treated in a nitrogen atmosphere at a temperature range of 1,000°C. or more and the calcination temperature or less. In addition,Japanese Unexamined Patent Publication No. 2011-174015 discloses amethod in which a calcined product obtained through calcination of rawmaterials is further heat-treated and then acid-treated. In addition,Japanese Unexamined Patent Publication No. 2007-326981 discloses amethod in which raw materials are powdered, the resulting powder isheated two or more times to obtain a β-sialon fluorescent material, orthe agglomerated powder is crushed during a period between the two ormore heating treatments, to produce a β-sialon fluorescent material.Besides, Japanese Unexamined Patent Publication No. 2013-173868discloses a method in which raw materials are calcined upon non-additionor addition with an activation agent-containing compound, and in thecase where the resulting calcined product is agglomerated, the calcinedproduct is crushed, ground, and/or classified as the need arises, and anactivation agent-containing compound in a larger amount than that at thetime of the first calcination is added to the calcined product which hasbeen subjected to crushing, grinding and/or classifying, followed byperforming second calcination.

SUMMARY

However, there is a need to improve the β-sialon fluorescent materialsin terms of the light emission luminance. In accordance with anembodiment of the present disclosure, an object thereof is to provide amethod of producing a β-sialon fluorescent material with a high lightemission intensity.

Measures for solving the aforementioned problems are as follows. Thepresent disclosure includes the following embodiments.

A first embodiment of the present disclosure concerns a method ofproducing a β-sialon fluorescent material, including preparing acalcined product having a composition of β-sialon containing anactivating element; grinding the calcined product to obtain a groundproduct; and heat-treating the ground product to obtain a heat-treatedproduct. A specific surface area of the ground product is 0.2 m²/g ormore.

A second embodiment of the present disclosure concerns a method ofproducing a β-sialon fluorescent material, including preparing acalcined product having a composition of β-sialon containing anactivating element; grinding the calcined product to obtain a groundproduct; and heat-treating the ground product to obtain a heat-treatedproduct. The grinding and heat-treating steps are repeated two times ormore in this order. In at least one grinding step, an average particlediameter of the ground product is 40 μm or less.

In accordance with the embodiments of the present disclosure, aproduction method from which a β-sialon fluorescent material with a highlight emission intensity is obtained can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing light emission spectra of β-sialonfluorescent materials according to an example of the present disclosureand a comparative example.

FIG. 2A is an SEM photograph of a ground product after a first grindingstep in the example of the present disclosure.

FIG. 2B is an SEM photograph of a ground product after a second grindingstep in the example of the present disclosure.

FIG. 2C is an SEM photograph of a β-sialon fluorescent material after anannealing step and a post-treatment step in the example of the presentdisclosure.

FIG. 3A is an SEM photograph of a ground product after a first grindingstep in the comparative example.

FIG. 3B is an SEM photograph of a ground product after a second grindingstep in the comparative example.

FIG. 3C is an SEM photograph of a β-sialon fluorescent material after anannealing step and a post-treatment step in the comparative example.

DETAILED DESCRIPTION

A method of producing a fluorescent material according to the presentdisclosure is hereunder described below. However, the embodiments shownbelow exemplify the method of producing a β-sialon fluorescent materialfor practicing the technical concept of the present invention, and thescope of the present invention is not limited to the method of producinga β-sialon fluorescent material shown below. In this specification, therelationship between the color name and the chromaticity coordinate, therelationship between the wavelength range of light and the color name ofmonochromic light, and the like are in accordance with JIS Z8110.

In this specification, the average particle diameter is a particlediameter (Dm; median diameter) at which the volume cumulative frequencyas measured with a laser diffraction particle size distributionmeasuring apparatus (for example, MASTER SIZER 3000, manufactured byMalvern Instruments, Ltd.) reaches 50% from the small diameter side. Inaddition, in this specification, the particle diameter D10 is a particlediameter at which the volume cumulative frequency as measured with theaforementioned apparatus reaches 10% from the small diameter side. Inaddition, in this specification, the particle diameter D90 is a particlediameter at which the volume cumulative frequency as measured with theaforementioned apparatus reaches 90% from the small diameter side.

Method of Producing β-Sialon Fluorescent Material

A method of producing a β-sialon fluorescent material according to thefirst embodiment of the present disclosure includes preparing a calcinedproduct having a composition of β-sialon containing an activatingelement; grinding the calcined product to obtain a ground product; andheat-treating the ground product to obtain a heat-treated product. Aspecific surface area of the ground product is 0.2 m²/g or more.

A method of producing a β-sialon fluorescent material according to thesecond embodiment of the present disclosure includes preparing acalcined product having a composition of β-sialon containing anactivating element; grinding the calcined product to obtain a groundproduct; and a heat-treating the ground product to obtain a heat-treatedproduct. The grinding and heat-treating steps are repeated two times ormore in this order. In at least one grinding step, an average particlediameter of the ground product is 40 μm or less.

Calcination Step

The method according to each of the first embodiment and the secondembodiment of the present disclosure includes preparing a calcinedproduct having a composition of β-sialon containing an activatingelement (the step is sometimes referred to as “calcination step”herein).

The calcined product can be obtained through calcination of a rawmaterial mixture. Examples of the raw material that constitutes the rawmaterial mixture include a compound containing an activating element anda compound containing elements that constitute a composition ofβ-sialon.

Compound Containing Elements that Constitute Composition of β-Sialon

Examples of the compound containing elements that constitute thecomposition of β-sialon include an aluminum compound, silicon nitride,compound containing activated element, and the like.

Aluminum Compound

Examples of the aluminum compound include an oxide, a hydroxide, anitride, an oxynitride, a fluoride, a chloride, and the like, eachcontaining aluminum. As the aluminum compound, an aluminum metalelemental substance or an aluminum alloy may be used, and an aluminummetal elemental substance or an aluminum alloy may also be used in placeof at least a part of the aluminum compound.

Specifically, examples of the aluminum compound may include aluminumnitride (AlN), aluminum oxide (Al₂O₃), aluminum hydroxide (Al(OH)₃), andthe like. The aluminum compound may be used alone, or may be used incombination of two or more thereof. For example, when two kinds ofaluminum compounds such as aluminum nitride and aluminum oxide are usedin combination, the molar ratio of aluminum nitride to aluminum oxide(AlN:Al₂O₃) is preferably in a range of 99:1 to 1:99, more preferably ina range of 97.5:2.5 to 75:25, and two kinds of aluminum compounds aremixed used.

Any average particle diameter of a usually used aluminum compound may beadopted. The average particle diameter of the aluminum compound ispreferably in a range of 0.01 μm or more and 20 μm or less, and morepreferably in a range of 0.1 μm or more and 10 μm or less.

The purity in the aluminum compound is preferably 95.0% by mass or more,more preferably 99.0% by mass or more, and still more preferably 99.5%by mass or more from the viewpoint of decreasing impurities other thanaluminum.

Silicon Nitride

The silicon nitride is a silicon compound containing a nitrogen atom anda silicon atom. A raw material of the silicon nitride may containsilicon oxide or may contain silicon oxynitride.

In the case where an oxygen atom is contained in the silicon nitride,the content of the oxygen atom is preferably 1.5% by mass or less, andpreferably 0.3% by mass or more, and more preferably 0.4% by mass ormore relative to the silicon nitride containing an oxygen atom (100% bymass).

As for the purity of the silicon nitride, from the viewpoint ofdecreasing impurities, it is preferred that the content of impuritiesother than oxygen be less than 1% by mass.

An average particle diameter of the silicon nitride is preferably in arange of 0.01 μm or more and 15.00 μm or less, more preferably in arange of 0.05 μm or more and 10.00 μm or less, and still more preferablyin a range of 0.10 μm or more and 5.00 μm or less.

The raw material mixture may further contain, in addition to the siliconnitride that is one compound containing elements that constitute thecomposition of β-sialon, a silicon compound, such as a silicon elementalsubstance and silicon oxide. Examples of the silicon compound includesilicon oxide, silicon oxynitride, and a silicate. An average particlediameter of the silicon elemental substance or silicon compound ispreferably in a range of 0.01 μm or more and 15.00 μm or less, morepreferably in a range of 0.05 μm or more and 10.00 μm or less, and stillmore preferably in a range of 0.10 μm or more and 5.00 μm or less.

Compound Containing Activating Element

The compound containing an activating element is contained in the rawmaterial mixture. The compound containing an activating element may beheat-treated together with the ground product, or may be annealedtogether with the heat-treated product. In this specification, thecompound, which is contained in the raw material mixture is alsoreferred to as a first compound containing an activating element; thecompound, which is heat-treated together with the ground product, isalso referred to as a second compound containing an activating element;and the compound, which is annealed together with the heat-treatedproduct, is also referred to as a third compound containing anactivating element.

The first compound containing an activating element, the second compoundcontaining an activating element, and the third compound containing anactivating element may be compounds, which are the same as or differentfrom each other.

The activating element is at least one element selected from the groupconsisting of Eu, Ce, Tb, Yb, Sm, Dy, Er, Mn, and Ag, preferably atleast one element selected from the group consisting of Eu, Ce, Tb, Yb,Sm, and Dy, and more preferably at least one element selected from thegroup consisting of Eu, Ce, Tb, and Yb.

Examples of the compound containing an activating element include anoxide, a hydroxide, a nitride, an oxynitride, a fluoride, and achloride, each containing an activating element. In addition, a metalelemental substance composed of an activating element or an alloycontaining an activating element in place of at least a part of thecompound containing an activating element may be used.

In the case where the compound containing an activating element is, forexample, europium (Eu), specifically, examples of the compoundcontaining europium include europium oxide (Eu₂O₃), europium nitride(EuN), and europium fluoride (EuF₃). Specifically, examples of othercompound containing an activating element include CeO₂, CeF₃, CeN,CeCl₃, Tb₂O₃, TbF₃, TbCl₃, Yb₂O₃, YbF₃, YbCl₃, Sm₂O₃, SmF₃, SmN, SmCl₃,Dy₂O₃, DyF₃, DyCl₃, Er₂O₃, ErCl₃, MnO₂, MnCl₂, Ag₂O, and AgCl. Thecompound containing an activating element may also be a hydrate. Inaddition, the compound containing an activating element may be usedalone, or may be used in combination of two or more thereof.

An average particle diameter of the compound containing an activatingelement is preferably in a range of 0.01 μm or more and 20.00 μm orless, and more preferably 0.10 μm or more and 10.00 μm or less.

The purity of the compound containing an activating element is typically95.0% by mass or more, and preferably 99.5% by mass or more from theviewpoint of decreasing impurities.

The compound containing an activating element may be contained in theraw material mixture in a ratio so as to satisfy the composition ofβ-sialon containing an activating element to be obtained. Alternatively,after obtaining the calcined product having the composition of β-sialoncontaining an activating element, taking into consideration the amountof the compound containing an activating element to be added in the heattreatment of the ground product or the annealing treatment of theheat-treated product, the compound containing an activating element maybe contained in the raw material mixture in a ratio smaller than that inthe composition of β-sialon containing an activating element to beobtained.

It is preferred that the amount of the first compound containing anactivating element, which is contained in the raw material mixture, belarger than the amount of the second compound containing an activatingelement. This is because, on the occasion of calcining the raw materialmixture to obtain a calcined product, the activating element in alargest amount is incorporated into the crystal of the calcined product.

In the case where a molar ratio of the activating element, which iscontained in the resulting β-sialon fluorescent material is defined as1, the amount of the first compound containing an activating elementwhich is contained in the raw material mixture is an amount ofpreferably more than 0.50 in terms of a molar ratio. The molar ratio isan amount of more preferably 0.55 or more, still more preferably 0.60 ormore, and especially preferably 0.65 or more.

A mixing ratio of the aluminum compound, the silicon nitride, and thecompound containing an activating element in the raw material mixturemay be properly adjusted according to the desired composition ofβ-sialon containing an activating element. In the case where the molaramount of the aluminum element, which is contained in the raw materialmixture is represented by z, a molar ratio of the silicon element to thealuminum element ((molar amount of Si):(molar amount of Al)) isrepresented by (6−z):z (0<z≤4.2), and preferably (0.01<z<1.0). A molarratio of a total molar amount of the silicon element and the aluminumelement to the activating element ((total molar amount of Si and Al)(molar amount of the activating element)) is, for example, preferably6:0.001 to 6:0.05, and more preferably 6:0.003 to 6:0.025.

The β-sialon fluorescent material preferably has a compositionrepresented by the following formula (Ip). In the formula (Ip), z is anumber satisfying an expression: 0<z≤4.2.

Si_(6-z)Al_(x)O_(z)N_(8-z):Eu  (Ip)

The raw material mixture may contain a β-sialon fluorescent materialthat is separately prepared, as the need arises. In the case where theβ-sialon fluorescent material is contained in the raw material mixture,its content is preferably in a range of 1% by mass or more and 50% bymass or less, more preferably in a range of 2% by mass or more and 40%by mass or less, and still more preferably in a range of 3% by mass ormore and 30% by mass or less in the total amount (100% by mass) of theraw material mixture.

The raw material mixture may contain a flux, such as a halide, as theneed arises. When the flux is contained in the raw material mixture, thereaction among the raw materials is promoted, and a solid phase reactionis readily advanced more uniformly. As for this matter, it may beconsidered that the temperature of the heat treatment in preparing acalcined product is substantially the same as or higher than theformation temperature of a liquid phase of a halide to be used as theflux, so that the reaction is promoted.

Examples of the halide include fluorides or chlorides of a rare earthmetal, an alkaline earth metal, or an alkali metal. In the case where ahalide of a rare earth metal is used as the flux, the flux can also beadded as the compound such that the calcined product has a desiredcomposition. For example, in the case where europium is contained in thedesired composition, europium fluoride that is the halide containingeuropium can be added as the flux.

In the case where the raw material mixture contains the flux, thecontent of the flux is preferably 20% by mass or less, and morepreferably 10% by mass or less, and preferably 0.1% by mass or more inthe raw material mixture (100% by mass).

As for the raw material mixture, after weighing the respective rawmaterials in a desired blending ratio, for example, the raw materialsmay be ground and mixed using a dry grinder, such as a ball mill, avibration mill, a hammer mill, a roll mill, and a jet mill; may beground and mixed using a mortar and a pestle; may be mixed using amixing machine, for example, a ribbon blender, a Henschel mixer, a Vtype blender, etc.; or may be ground and mixed using both a dry grinderand a mixing machine. In addition, the mixing may be achieved by meansof either dry mixing or wet mixing upon addition of a solvent or thelike.

The raw material mixture may be charged in, for example, a boronnitride-made crucible and then calcined.

The calcination temperature for calcining the raw material mixture toobtain a calcined product is preferably in a range of 1,850° C. orhigher and 2,100° C. or lower, more preferably in a range of 1,900° C.or higher and 2,050° C. or lower, still more preferably in a range of1,920° C. or higher and 2,050° C. or lower, and especially preferably ina range of 2,000° C. or higher and 2,050° C. or lower.

When the raw material mixture is calcined at the predeterminedtemperature or higher, the calcined product having a composition ofβ-sialon containing an activating element is efficiently formed, and theactivating element is readily incorporated into the crystal of thecalcined product having a composition of β-sialon. In addition, when theraw material mixture is calcined at the predetermined temperature orlower, the decomposition of the calcined product having a composition ofβ-sialon is suppressed.

The atmosphere where the raw material mixture is calcined is preferablyan atmosphere containing a nitrogen gas, and the content of the nitrogengas in the atmosphere is preferably 90% by volume or more, and morepreferably 95% by volume or more. In the case where the atmosphere wherethe raw material mixture is calcined is an atmosphere containing anitrogen gas, other gas, such as hydrogen, oxygen, and ammonia, may becontained in addition to the nitrogen gas.

The pressure at which the raw material mixture is calcined is notparticularly limited so long as the desired calcined product isobtained. It is preferred that the pressure at which the raw materialmixture is calcined be a relatively high pressure from the viewpoint ofsuppressing the decomposition of the resulting calcined product. Thepressure at which the raw material mixture is calcined is preferably ina range of atmospheric pressure (about 0.1 MPa) or more and 200 MPa orless, more preferably in a range of 0.3 MPa or more and 100 MPa or less,and still more preferably in a range of 0.5 MPa or more and 50 MPa orless. The pressure is especially preferably in a range of 0.6 MPa ormore and 1.2 MPa or less from the viewpoint of restriction on industrialequipment.

In the calcination step, before the temperature of the resultingcalcined product is lowered to room temperature, a first holding step ofholding the calcined product at a predetermined temperature that ishigher than room temperature and lower than the calcination temperaturemay be provided. The temperature of the first holding step is preferablyin a range of 1,000° C. or higher and lower than 1,800° C., and morepreferably in a range of 1,200° C. or higher and 1,700° C. or lower. Thetime of the first holding step is preferably in a range of 0.1 hours ormore and 20 hours or less, and more preferably in a range of 1 hour ormore and 10 hours or less. When the first holding step of holding thecalcined product is provided, the reaction of the raw material mixtureis advanced, and the activating element is readily incorporated into thecrystal of the calcined product.

The temperature lowering time for lowering the temperature of theresulting calcined product to room temperature is preferably in a rangeof 0.1 hours or more and 20 hours or less, more preferably in a range of1 hour or more and 15 hours or less, and still more preferably in arange of 3 hours or more and 12 hours or less. When the temperaturelowering time is set to a fixed level or more, the activating element isreadily incorporated into the crystal of the calcined product during thetemperature lowering.

Grinding Step

The method of producing a β-sialon fluorescent material according toeach of the first embodiment and the second embodiment of the presentdisclosure includes grinding the calcined product to obtain a groundproduct (sometimes referred to as “grinding step” herein).

In the first embodiment and the second embodiment of the presentdisclosure, grinding the calcined product to obtain a ground productmeans not only coarse grinding or crushing of a powdered agglomerateresulting from agglomeration of powders of the calcined product but alsostrong grinding until the calcined product becomes a ground producthaving a predetermined size.

In the grinding step according to the first embodiment of the presentdisclosure, a specific surface area of the resulting ground product is0.20 m²/g or more. The specific surface area of the resulting groundproduct is preferably 0.25 m²/g or more, more preferably 0.28 m²/g ormore, and still more preferably 0.29 m²/g or more.

When the specific surface area of the ground product is less than 0.20m²/g, the ground product becomes excessively large; even whenheat-treated in a heat treatment step as mentioned later, arearrangement reaction of crystal is hardly caused; the activatingelement is hardly incorporated into the crystal; and it becomesdifficult to enhance the light emission intensity.

In the method of producing a β-sialon fluorescent material according tothe second embodiment of the present disclosure, a specific surface areaof the ground product having been subjected to strong grinding ispreferably 0.20 m²/g or more, more preferably 0.25 m²/g or more, stillmore preferably 0.28 m²/g or more, and especially preferably 0.29 m²/gor more. When the calcined product is ground such that the specificsurface area is 0.20 m²/g or more, and after grinding, the groundproduct is again subjected to a heat treatment as mentioned later, thecrystal is rearranged, and on the occasion when the crystal isrearranged, the activating element is readily incorporated into thecrystal, and a β-sialon fluorescent material having a high relativelight emission intensity and an excellent light emission luminance canbe obtained.

In the method of producing a β-sialon fluorescent material according tothe second embodiment of the present disclosure, with respect to thegrinding step to be performed two or more times, it is preferred that inthe at least one grinding step, the strong grinding be performed suchthat the specific surface area of the ground product is 0.35 m²/g ormore, and it is more preferred that in at least one grinding step, thestrong grinding be performed such that the specific surface area of theground product is 0.37 m²/g or more.

Though an upper limit value of the specific surface area of the groundproduct obtained in the grinding step is not particularly limited, whenthe specific surface area is made excessively large, it takes time andenergy for achieving the grinding, and the production becomescomplicated. Therefore, the specific surface area of the ground productis preferably 1.00 m²/g or less, more preferably 0.95 m²/g or less, andstill more preferably 0.90 m²/g or less.

It is preferred that the calcined product be ground using a dry grinder,such as a ball mill, a vibration mill, a hammer mill, a roll mill, and ajet mill.

As for the calcined product, there is a case where the powders of thecalcined product form a powdered agglomerate. In the grinding step, itis preferred that the calcined product, which has become the resultingpowdered agglomerate, be crushed or coarsely ground using a mortar and apestle, or the like to such an extent that the average particle diameteris several tens μm, specifically the average particle diameter is morethan 20 μm and less than 100 μm, and the resultant is then ground usingthe aforementioned dry grinder or the like so as to have a predeterminedspecific area.

The grinding step may include a step of performing classification bypassing through the ground product obtained by means of dry sieving orthe like.

An average particle diameter (Dm) of the ground product is preferably ina range of 5 μm or more and 40 μm or less, more preferably in a range of8 μm or more and 30 μm or less, and still more preferably in a range of10 μm or more and 20 μm or less. When the average particle diameter (Dm)of the ground product falls within the aforementioned range, it may beconsidered that in the heat-treated product obtained by a heat treatmentstep as mentioned later, when the small particle comes into contact withthe large particle, the small particle is easy to grow to an extent thatthe size of the particle becomes a desired size, as compared with thecase where the large particles come into contact with each other. Inaddition, it may be considered that the rearrangement of crystal isreadily caused on the contact surface between the small particle and thelarge particle at the time of heat treatment, and on the occasion whenthe crystal is rearranged, the activating element is readilyincorporated into the crystal. As a result, it may be considered thatthe light emission intensity can be enhanced.

In the method of producing a β-sialon fluorescent material according tothe second embodiment of the present disclosure, the grinding and heattreatment steps are repeated two times or more in this order, and in atleast one grinding step, an average particle diameter of the groundproduct is 40 μm or less. The average particle diameter (Dm) of theground product in at least one grinding step being more than 40 μm isnot preferred because the contact between the small particle and thelarge particle is hardly caused; the particle hardly grows; therearrangement of crystal is hardly caused on the contact surface betweenthe small particle and the large particle at the time of heat treatment;and the activating element is hardly incorporated into the crystal.

The particle diameter D10 of the ground product, at which the volumecumulative frequency reaches 10% from the small diameter side in theparticle size distribution, is preferably in a range of 1 μm or more and12 μm or less, more preferably in a range of 2 μm or more and 11 μm orless, and still more preferably in a range of 3 μm or more and 10.5 μmor less. When the D10 of the ground product falls within theaforementioned range, the ground product is strongly ground, and theground product having a fine particle diameter is contained. Therefore,by performing a heat treatment as mentioned later, on the occasion whenthe ground products react with each other, and the crystal isrearranged, the activating element is readily incorporated into thecrystal, and the light emission intensity can be enhanced.

The particle diameter D90 of the ground product, at which the volumecumulative frequency reaches 90% from the small diameter side in theparticle size distribution, is preferably in a range of 15 μm or moreand 50 μm or less, more preferably in a range of 18 μm or more and 45 μmor less, and still more preferably in a range of 20 μm or more and 40 μmor less. When the D90 of the ground product falls within theaforementioned range, the relatively large particle is contained in theground product together with the small particle, and the reactionbetween the small particle and the large particle is more advanced by aheat treatment as mentioned later to cause the rearrangement of crystal;and not only the activating element is readily incorporated into therearranged crystal, but also the heat-treated product can be grown to adesired size, and the light emission intensity can be enhanced.

Heat Treatment Step

The method of producing a β-sialon fluorescent material according toeach of the first embodiment and the second embodiment of the presentdisclosure includes heat-treating the ground product to obtain aheat-treated product (sometimes referred to as “heat treatment step”herein).

In the method of producing a β-sialon fluorescent material according anembodiment of the present disclosure, due to the heat treatment step ofagain heat-treating the ground product, which has been ground so as tohave a predetermined surface area, on the occasion when the crystal isrearranged, the activating element is readily incorporated into thecrystal, and the light emission intensity can be enhanced.

A heat treatment temperature in the heat treatment step is preferably ina range of 1,850° C. or higher and 2,100° C. or lower, more preferablyin a range of 1,900° C. or higher and 2,080° C. or lower, still morepreferably in a range of 1,920° C. or higher and 2,050° C. or lower, andespecially preferably in a range of 1,970° C. or higher and 2,040° C. orlower. It is preferred that the heat treatment temperature in the heattreatment step be the same as the heat treatment temperature in thecalcination step, or a temperature lower than the heat treatmenttemperature in the calcination step. In the case where there is atemperature difference between the heat treatment temperature in thecalcination step and the heat treatment temperature in the heattreatment step, the temperature difference is preferably 10° C. or more,and more preferably 20° C. or more, and an upper limit of thetemperature difference is preferably 100° C. or less.

The atmosphere where the ground product is heat-treated is preferably aninert gas atmosphere. The inert gas atmosphere as referred to in thisspecification means an atmosphere containing, as a main component,argon, helium, nitrogen, or the like. Though there is a case where theinert gas atmosphere contains oxygen as an inevitable impurity, so longas the concentration of oxygen contained in an atmosphere is 15% byvolume or less, such an atmosphere is included as the inert gasatmosphere. The concentration of oxygen in the inert gas atmosphere ispreferably 10% by volume or less, more preferably 5% by volume or less,and still more preferably 1% by volume or less. When the oxygenconcentration is the predetermined value or more, there is a concernthat the heat-treated product is excessively oxidized.

It is preferred that the inert gas atmosphere where the ground productis heat-treated be an atmosphere containing a nitrogen gas. The contentof the nitrogen gas in the inert gas atmosphere is preferably 90% byvolume or more, and more preferably 95% by volume or more. In the casewhere the atmosphere where the raw material mixture is calcined is anatmosphere containing a nitrogen gas, it may contain, in addition to thenitrogen gas, other gas than the nitrogen gas, such as hydrogen andammonia. Hydrogen or hydrogen, which is produced through decompositionof ammonia, has a reducing action and is easy to reduce the activatingelement, for example, to reduce the valence of Eu from trivalent todivalent as a center of light emission, and the light emission intensitycan be enhanced.

It is preferred that the pressure at which the ground product isheat-treated be a relatively high pressure from the viewpoint ofsuppressing the decomposition of the resulting heat-treated product. Thepressure at which the ground product is heat-treated is preferably in arange of atmospheric pressure (about 0.1 MPa) or more and 200 MPa orless, more preferably in a range of 0.3 MPa or more and 100 MPa or less,and still more preferably in a range of 0.5 MPa or more and 50 MPa orless. The pressure is especially preferably in a range of 0.6 MPa ormore and 1.2 MPa or less from the viewpoint of restriction on industrialequipment.

As for the heat treatment of the ground product, it is preferred that,after elevating the temperature to a predetermined heat treatmenttemperature, the heat treatment be performed at the predetermined heattreatment temperature for a fixed time. The heat treatment time ispreferably in a range of 1 hour or more and 48 hours or less, morepreferably in a range of 2 hours or more and 24 hours or less, and stillmore preferably in a range of 3 hours or more and 20 hours or less. Whenthe heat treatment time is the predetermined value or more, on theoccasion when the elements in the ground product are again rearrangedinto a crystal structure due to the heat treatment, the activatingelement is readily incorporated into the crystal to be rearranged. Whenthe heat treatment time is the predetermined value or less, thedecomposition of the crystal structure of the heat-treated product canbe suppressed.

In the heat treatment step, before the temperature of the resultingheat-treated product is lowered to room temperature, a second holdingstep of holding the heat-treated product at a predetermined temperaturethat is higher than room temperature and lower than the heat treatmenttemperature may be provided. The temperature of the second holding stepis preferably in a range of 1,000° C. or higher and lower than 1,800°C., and more preferably in a range of 1,200° C. or higher and 1,700° C.or lower. The time of the second holding step is preferably in a rangeof 0.1 hours or more and 20 hours or less, and more preferably in arange of 1 hour or more and 10 hours or less. When the second holdingstep of holding the heat-treated product is provided, the reaction ofthe heat-treated product is advanced, and the activating element isreadily incorporated into the crystal resulting from rearrangement ofthe heat-treated product.

The temperature lowering time for lowering the temperature of theresulting heat-treated product to room temperature is preferably in arange of 0.1 hours or more and 20 hours or less, more preferably in arange of 1 hour or more and 15 hours or less, and still more preferablyin a range of 3 hours or more and 12 hours or less. When the temperaturelowering time is the predetermined value or more, the activating elementis readily incorporated into the crystal resulting from rearrangement ofthe heat-treated product during the temperature lowering. Even when thetemperature lowering time is made excessively long, the incorporation ofthe activating element to an extent of more than a certain degree cannotbe expected. Therefore, when the temperature lowering time is set to thepredetermined value or less, the wasteful production time consumptioncan be eliminated, and the activating element can be incorporated intothe crystal resulting from rearrangement of the heat-treated product.

In the heat treatment step, it is preferred to heat-treat the groundproduct together with the second compound containing an activatingelement.

So long as the β-sialon fluorescent product having the desiredcomposition is obtained, the second compound containing an activatingelement may be a compound the same as or different from the firstcompound containing an activating element which is contained in the rawmaterial mixture.

It is preferred that the amount of the second compound containing anactivating element be smaller than the amount of the first compoundcontaining an activating element which is contained in the raw materialmixture. This is because that it may be considered that, as comparedwith the second activating element that performs the heat treatment inthe heat treatment step together with the ground product, the activatingelement (first activating element) which is contained in the rawmaterial mixture can be contained more efficiently in the crystalstructure of the β-sialon fluorescent material.

In the case where a molar ratio of the activating element which iscontained in the resulting β-sialon fluorescent material is defined as1, the amount of the second compound containing an activating elementwhich is heat-treated together with the ground product is an amount ofpreferably less than 0.50 in terms of a molar ratio. The molar ratio isan amount of more preferably 0.45 or less, still more preferably 0.40 orless, and especially preferably 0.35 or less.

In the method of producing a β-sialon fluorescent material according tothe second embodiment of the present disclosure, the grinding and heattreatment steps are repeated two times or more in this order.

In the method of producing a β-sialon fluorescent material according tothe second embodiment of the present disclosure, by repeating thegrinding and heat treatment steps in this order, the crystal in theheat-treated product is rearranged, and on the occasion when the crystalis rearranged, the activating element is readily incorporated into thecrystal, and the light emission intensity can be enhanced.

Annealing Treatment Step

It is preferred that the method of producing a β-sialon fluorescentmaterial according to each of the first embodiment and the secondembodiment of the present disclosure include an annealing treatment stepof annealing the heat-treated product in a noble gas atmosphere at atemperature that is lower than the heat treatment temperature in theheat treatment step, to obtain an annealed product.

In the method of producing a β-sialon fluorescent material according toan embodiment of the present disclosure, at least a part of an unstablecrystal portion existing in the heat-treated product, such as anon-crystalline portion, can be decomposed by the annealing treatmentstep of annealing the heat-treated product, and a content proportion ofthe stable crystal structure into which the activating element has beenincorporated can be increased, thereby enhancing the light emissionintensity.

As for the noble gas atmosphere in the annealing treatment step, atleast one noble gas, such as helium, neon, and argon, has only to becontained in the atmosphere, and it is preferred that at least argon becontained in the atmosphere. The noble gas atmosphere may contain, inaddition to the noble gas, oxygen, hydrogen, nitrogen. The content ofthe noble gas in the noble gas atmosphere is preferably 95% by volume ormore, and more preferably 99% by volume or more.

In the case of performing the annealing treatment in the noble gasatmosphere, the pressure is preferably in a range of atmosphericpressure (about 0.1 MPa) or more and 1 MPa or less, more preferably in arange of atmospheric pressure or more and 0.5 MPa or less, and stillmore preferably in a range of atmospheric pressure or more and 0.2 MPaor less.

The annealing treatment of the heat-treated product may be performedunder reduced pressure that is lower than the atmospheric pressure, andmay also be performed in vacuum. In the case of performing the annealingtreatment in vacuum, the pressure is, for example, 10 kPa or less,preferably 1 kPa or less, and more preferably 100 Pa or less. Here, theterms “under reduced pressure” or “in vacuum” do not exclude thepresence of a gas at the time of annealing treatment, and a gas, such asa noble gas, nitrogen, hydrogen, and oxygen may exist even in theannealing treatment under reduced pressure or in vacuum.

The annealing treatment temperature is preferably in a range of 1,300°C. or higher and 1,600° C. or lower, and more preferably in a range of1,350° C. or higher and 1,500° C. or lower. It is preferred that theannealing treatment temperature in the annealing treatment step be lowerthan the calcination temperature. In addition, it is preferred that theannealing treatment temperature be lower than the heat treatmenttemperature. In the annealing treatment step, by setting the temperatureto the predetermined temperature range, an unstable phase which iscontained in the heat-treated product, for example, a non-crystallineportion, a low crystalline portion with high dislocation density anddefect density, can be efficiently thermally decomposed, and a highcrystalline β-sialon fluorescent material having a large contentproportion of the stable crystal structure can be obtained.

In the annealing treatment step, it is preferred that, after elevatingthe temperature to the predetermined annealing treatment temperature,this temperature be held for a fixed time.

The annealing treatment time is preferably in a range of 1 hour or moreand 48 hours or less, more preferably in a range of 2 hours or more and24 hours or less, and still more preferably in a range of 3 hours ormore and 20 hours or less. When the annealing treatment temperature isthe predetermined value or more, an unstable phase which is contained inthe heat-treated product, for example, a non-crystalline portion, a lowcrystalline portion, is readily decomposed, and when the annealingtreatment temperature is the predetermined value or less, thedecomposition of the crystal structure can be suppressed.

In the annealing treatment step, before the temperature of the resultingheat-treated product is lowered to room temperature, a third holdingstep of holding the heat-treated product at a predetermined temperaturethat is higher than room temperature and lower than the annealingtreatment temperature may be provided. The temperature of the thirdholding step is preferably in a range of 800° C. or higher and lowerthan 1,600° C., and more preferably in a range of 1,000° C. or higherand 1,400° C. or lower. The time of the third holding step is preferablyin a range of 0.5 hours or more and 20 hours or less, and morepreferably in a range of 1 hour or more and 10 hours or less. Byproviding the third holding step, the unstable phase is readilydecomposed.

The temperature lowering time for lowering the temperature of theresulting annealed product to room temperature is preferably in a rangeof 0.1 hours or more and 20 hours or less, more preferably in a range of1 hour or more and 15 hours or less, and still more preferably in arange of 3 hours or more and 12 hours or less. According to this, theunstable phase is readily decomposed during the temperature lowering.

In the annealing treatment step, it is preferred to anneal theheat-treated product together with a compound containing an activatingelement (the third compound containing an activating element).

So long as the β-sialon fluorescent material having the desiredcomposition is obtained, the third compound containing an activatingelement may be a compound the same as or different from the firstcompound containing an activating element which is contained in the rawmaterial mixture, or the second compound containing an activatingelement which is heat-treated together with the heat-treated product.

It is preferred that the amount of the third compound containing anactivating element be smaller than that of the first compound containingan activating element which is contained in the raw material mixture.

As for the third compound containing an activating element, first ofall, a part of the third compound containing an activating element isreduced together with the heat-treated product through the annealingtreatment in a noble gas atmosphere, thereby producing an activatingelement elemental substance or a gaseous material containing an ion ofthe activating element with a valence having an energy level as a centerof light emission. Subsequently, this gaseous material comes intocontact with the heat-treated product, whereby the activating elementcontained in the heat-treated product is reduced into the activatingelement with a valence having an energy level as a center of lightemission. Furthermore, it may be considered that the activating elementhaving an energy level as a center of light emission, which is containedin the gaseous material, is also readily incorporated into the annealedproduct. In this way, the activating element as a center of lightemission is efficiently incorporated into the β-sialon fluorescentmaterial, and as a result, the β-sialon fluorescent material with a highlight emission intensity can be obtained.

In the case where the activating element is, for example, Eu, first ofall, in the annealing treatment step, by annealing a compound containingEu (for example, Eu₂O₃) together with the heat-treated product,trivalent Eu in Eu₂O₃ is reduced to produce Eu or a gaseous materialcontaining Eu²⁺. Subsequently, due to Eu in the gaseous material, notonly Eu³⁺ contained in the heat-treated product is reduced into Eu²⁺,but also the resulting Eu²⁺ or Eu²⁺ produced in the gaseous material isincorporated into the annealed product, and a β-sialon fluorescentmaterial containing a plenty of Eu²⁺ serving as a center of lightemission is readily produced.

The amount of the third compound containing an activating element to beannealed together with the heat-treated product is preferably 0.01 partsby mass or more, more preferably 0.05 parts by mass or more, and stillmore preferably 0.1 parts by mass or more on the basis of theheat-treated product (100 parts by mass). In addition, the amount of thethird compound containing an activating element is preferably 50 partsby mass or less, more preferably 20 parts by mass or less, still morepreferably 15 parts by mass or less, and especially preferably 10 partsby mass or less on the basis of the heat-treated product (100 parts bymass).

In the annealing treatment step, it is preferred that the third compoundcontaining an activating element be annealed in such a manner that thegaseous material, from which the third compound containing an activatingelement is produced, is able to come into contact with the heat-treatedproduct. In this case, the heat-treated product and the third compoundcontaining an activating element may be charged, in a mixed or non-mixedstate, in the same vessel, followed by annealing, and may also becharged, in a non-mixed state, in separate vessels, respectively,followed by annealing. In addition, a part of the third compoundcontaining an activating element to be used and the heat-treated productmay be charged, in a mixed or non-mixed state, in the same vessel, andthe remaining third compound containing an activating element may becharged in a separate vessel, following by annealing. In the case ofmixing the heat-treated product and the third compound containing anactivating element, it is preferred to mix them uniformly as far aspossible.

Classification Step

In the method of producing a β-sialon fluorescent material, after theannealing treatment step, the resulting annealed product is crushed orground, and thereafter, a classification step of performingclassification may be included.

As for crushing or grinding, which is performed before theclassification step, the annealed product can be crushed or ground in adesired size by using a dry grinder, for example, a ball mill, avibration mill, a hammer mill, a roll mill, a jet mill. Alternatively,the annealed product may also be crushed or ground in a desired size byusing a mortar and a pestle. The grinding, which is performed after theannealing treatment step but before the classification step, meanscrushing or grinding of the agglomerate resulting from agglomeration bythe annealing treatment and excludes strong grinding to be performedsuch that the specific surface area of the ground annealed product is0.2 m²/g or more.

Post-Treatment Step

The method of producing a β-sialon fluorescent material may include apost-treatment step for post-treating the heat-treated product orannealed product. Examples of the post-treatment step include an acidtreatment step, a base treatment step, and a fluorine treatment step asmentioned below, and the like.

There is a case where a thermally decomposed product produced in thecalcination step or heat treatment step, such as a silicon elementalsubstance, is contained in the heat-treated product or annealed product.By performing the post-treatment step, the thermally decomposed product,such as a silicon elemental substance, can be removed. Though it may beconsidered that the silicon elemental substance absorbs a part of thelight emission of the β-sialon fluorescent material, by removing such athermally decomposed product, the light emission intensity of theβ-sialon fluorescent material can be more enhanced.

Acid Treatment Step

As for the post-treatment step, it is preferred that the heat-treatedproduct or annealed product be brought into contact with an acidicsolution. This post-treatment step is sometimes referred to as an acidtreatment step.

As for the acid treatment step, the heat-treated product may be broughtinto contact with an acidic solution without going through the annealingtreatment step, and the annealed product having going through theannealing treatment step may be brought into contact with an acidicsolution.

The content of the thermally decomposed product contained in theheat-treated product or annealed product can be decreased by the acidtreatment step.

An acidic substance which is contained in the acidic solution may be aninorganic acid, such as hydrofluoric acid and nitric acid, or hydrogenperoxide.

The acidic solution is preferably an acidic solution containing at leastone selected from hydrofluoric acid and nitric acid, and more preferablya mixed acid solution containing both hydrofluoric acid and nitric acid.The acidic solution may also contain, in addition to hydrofluoric acidand nitric acid, hydrochloric acid.

Base Treatment Step

It is preferred that the method of producing a β-sialon fluorescentmaterial according to an embodiment of the present disclosure include apost-treatment step of bringing the heat-treated product or annealedproduct into contact with a basic substance. This post-treatment step issometimes referred to as a base treatment step.

As for the base treatment step, the heat-treated product may be broughtinto contact with a basic substance without going through the annealingtreatment step, and the annealed product having gone through theannealing treatment step may be brought into contact with a basicsubstance.

The content of the thermally decomposed product contained in theheat-treated product or annealed product can be decreased by the basetreatment step.

The basic substance is preferably at least one selected from the groupconsisting of LiOH, NaOH, KOH, RbOH, CsOH, and NH₃, and more preferablyat least one of NaOH and KOH.

Fluorine Treatment Step

The method of producing a β-sialon fluorescent material according to anembodiment of the present disclosure may include a post-treatment stepof bringing the heat-treated product or annealed product into contactwith a fluorine-containing substance. This post-treatment step issometimes referred to as a fluorine treatment step. As thefluorine-containing substance which is used in the fluorine treatmentstep, hydrofluoric acid which is used for the acidic solution in theacid treatment step is excluded.

As for the fluorine treatment step, the heat-treated product may bebrought into contact with a fluorine-containing substance without goingthrough the annealing treatment step, and the annealed product havinggone through the annealing treatment step may be brought into contactwith a fluorine-containing substance.

The content of the thermally decomposed product contained in theheat-treated product or annealed product can be decreased by thefluorine treatment step.

The fluorine-containing substance is preferably at least one selectedfrom the group consisting of F₂, CHF₃, CF₄, NH₄HF₂, NH₄F, SiF₄, KrF₂,XeF₂, XeF₄, and NF₃.

The fluorine-containing substance is more preferably a fluorine gas (F₂)or aluminum fluoride (NH₄F). The fluorine-containing substance is notrequired to be a gas. For example, though NH₄HF₂, NH₄F, and the like area solid, a gas containing a fluorine element is released in the fluorinetreatment step, and the content of the thermally decomposed productwhich is contained in the heat-treated product or annealed product canbe decreased by this gas containing a fluorine element.

The atmosphere where the heat-treated product or annealed product isbrought into contact with the fluorine-containing substance ispreferably an inert gas atmosphere. By bringing the heat-treated productor annealed product into contact with the fluorine-containing substancein the inert gas atmosphere, the thermally decomposed product which iscontained in the heat-treated product or annealed product can be moreefficiently removed.

Classification Step, Etc. After Post-Treatment Step

After the heat treatment step, the resulting β-sialon fluorescentmaterial can be subjected to a crushing treatment, a grinding treatment,a classification treatment, and so on.

EXAMPLES

The present disclosure will be more specifically described by way ofExamples, but the present disclosure will not be limited to theseExamples.

Example 1

Silicon nitride (Si₃N₄), aluminum nitride (AlN), aluminum oxide (Al₂O₃)and europium oxide (Eu₂O₃) were weighed in a molar ratio of Si:Al:Eu of5.75:0.25:0.01 and mixed to obtain a raw material mixture. At that time,aluminum nitride and aluminum oxide (AlN:Al₂O₃) were weighed and mixedso that the molar ratio was 89.5:10.5.

This raw material mixture was charged in a boron nitride-made crucibleand calcined in a nitrogen atmosphere (nitrogen: 99% by volume or more)at 0.92 MPa (gauge pressure) and 2,030° C. for 10 hours, therebyobtaining a calcined product.

The resulting calcined product was coarsely ground using a mortar and apestle and then subjected to a first grinding treatment by means ofstrong grinding for 20 hours by using a ball mill using two kinds ofsilicon nitride-made balls having a diameter (ϕ) of 20 mm and a diameter(ϕ) of 25 mm, respectively and a ceramic pot, thereby obtaining a groundproduct. In the first grinding step, 0.0015 mols of europium oxide(Eu₂O₃) was added to 1 mol of the calcined product, and the grindingtreatment was performed.

Subsequently, the resulting ground product was charged in a boronnitride-made crucible and then subjected to a first heat treatment in anitrogen atmosphere (nitrogen: 99% by volume or more) at 0.92 MPa (gaugepressure) and 2,000° C. for 10 hours, thereby obtaining a heat-treatedproduct. The resulting heat-treated product was subjected to temperaturelowering to room temperature for 5 hours.

Subsequently, the resulting heat-treated product was subjected to asecond grinding treatment under the same conditions as those in thefirst grinding step, thereby obtaining a ground product. In the secondgrinding step, 0.001 mols of europium oxide (Eu₂O₃) was added to 1 molof the calcined product, and the grinding treatment was performed.

Subsequently, the resulting ground product was subjected to a secondheat treatment under the same conditions as those in the first heattreatment step, thereby obtaining a heat-treated product. The resultingheat-treated product was subjected to temperature lowering to roomtemperature for 5 hours.

Relative to 100 parts by mass of the resulting heat-treated product, 0.5parts by mass of europium oxide (Eu₂O₃) was weighed and added to theheat-treated product, thereby obtaining a mixture.

Subsequently, the resulting mixture was subjected to an annealingtreatment in an argon atmosphere at atmospheric pressure (about 0.1 MPa)and 1,400° C. for 5 hours.

In the annealing treatment step, on the way of temperature lowering ofthe annealed product from the annealing treatment temperature to roomtemperature, the annealed product was held at 1,100° C. for 5 hours, andafter going through this holding step, the annealed product wasobtained.

Subsequently, the annealed product was crushed or ground and thendispersed to achieve a classification treatment.

Subsequently, the annealed product having been subjected to theclassification treatment was put into a mixed acid solution obtained bymixing hydrofluoric acid (HF: 50% by mass) and nitric acid (HNO₃: 60% bymass) in a ratio of 1:1 (mass ratio), and the contents were stirred at50° C. for 30 minutes, followed by washing and drying to produce aβ-sialon fluorescent material.

Example 2

A β-sialon fluorescent material was produced in the same manner as inExample 1, except that the grinding time in the second grinding step waschanged to 40 hours.

Example 3

A β-sialon fluorescent material was produced in the same manner as inExample 1, except that the grinding time in the second grinding step waschanged to 60 hours.

Example 4

A β-sialon fluorescent material was produced in the same manner as inExample 1, except that the grinding time in the first grinding step waschanged to 40 hours, and that the grinding time in the second grindingstep was changed to 40 hours.

Example 5

A β-sialon fluorescent material was produced in the same manner as inExample 1, except that the grinding time in the first grinding step waschanged to 60 hours.

Example 6

A β-sialon fluorescent material was produced in the same manner as inExample 1, except that the second grinding step and the second heattreatment step were not performed.

Comparative Example 1

A β-sialon fluorescent material was produced in the same manner as inExample 1, except that in the first grinding step and the secondgrinding step, a ball mill in which the ceramic pot was replaced by apolypropylene-made vessel was used, and that the grinding time waschanged to 0.5 hours.

Evaluation Surface Area

In each of the Examples and Comparative Example, with respect to theground product obtained in the first grinding step, the ground productobtained in the second grinding step, and the β-sialon fluorescentmaterial, a specific surface area was measured with an automaticspecific surface area measurement apparatus (GEMINI 2375, manufacturedby Micromeritics) by the BET method.

Average Particle Diameter

In the Examples and Comparative Example, with respect to each of theground products obtained in the first grinding step, the ground productsobtained in the second grinding step, and the β-sialon fluorescentmaterials, an average particle diameter (Dm: median diameter) at whichthe volume cumulative frequency reaches 50% from the small diameterside, a particle diameter (D10) at which the volume cumulative frequencyreaches 10% from the small diameter side, and a particle diameter (D90)at which the volume cumulative frequency reaches 90% from the smalldiameter side were measured with a laser diffraction particle sizedistribution measuring apparatus (product name: MASTER SIZER 3000,manufactured by Malvern Instruments, Ltd.). In addition, a standarddeviation (a) was calculated from the particle size distribution of themeasured β-sialon fluorescent material. The results are shown in Table1.

Light Emission Characteristics

With respect to the β-sialon fluorescent material of each of theExamples and Comparative Example, the light emission characteristicswere measured. The light emission characteristics of the β-sialonfluorescent material were measured with a spectrofluorophotometer(QE-2000, manufactured by Otsuka Electronics Co., Ltd.) at a wavelengthof excitation light of 450 nm. The energy of the resulting lightemission spectrum (relative light emission intensity, %) was obtained.The results are shown in the following Table 1. The relative lightemission intensity was calculated based on the β-sialon fluorescentmaterial of Comparative Example 1 as 100%. In addition, FIG. 1 shows thelight emission spectrum (the relation between the wavelength (nm) andthe relative light emission intensity (%)) of each of Example 1 andComparative Example 1.

SEM Image

SEM images of the β-sialon fluorescent materials of Example 1 andComparative Example 1 were obtained with a scanning electron microscope(SEM).

FIG. 2A is an SEM photograph of the ground product after the firstgrinding step in Example 1, FIG. 2B is an SEM photograph of the groundproduct after the second grinding step in Example 1, and FIG. 2C is anSEM photograph of the β-sialon fluorescent material after the annealingstep and the post-treatment step in Example 1.

FIG. 3A is an SEM photograph of the ground product after the firstgrinding step in Comparative Example 1, FIG. 3B is an SEM photograph ofthe ground product after the second grinding step in Comparative Example1, and FIG. 3C is an SEM photograph of the β-sialon fluorescent materialafter the annealing step and the post-treatment step in ComparativeExample 1.

TABLE 1 β-Sialon fluorescent material First ground product Second groundproduct Relative Specific Specific Particle diameter (μm) light surfacesurface σ emission Grinding Particle diameter (μm) area GrindingParticle diameter (μm) area (Standard intensity (hr) Dm D10 D90 (m²/g)(hr) Dm D10 D90 (m²/g) Dm deviation) D10 D90 (%) Example 1 20 19.7 9.335.5 0.311 20 18.9 10.4 32.2 0.294 25.8 0.335 16.9 39.3 103.9 Example 220 19.2 9.0 34.2 0.355 40 16.9 8.9 28.5 0.394 25.8 0.329 16.9 38.7 105.9Example 3 20 19.7 9.2 35.5 0.305 60 11.3 4.1 20.1 0.862 25.2 0.347 16.239.0 106.6 Example 4 40 16.5 7.7 29.5 0.388 40 16.3 8.4 28.5 0.370 26.30.356 16.8 40.9 107.1 Example 5 60 12.1 4.5 23.5 0.761 20 16.6 9.5 26.50.353 26.9 0.361 17.1 42.2 106.9 Example 6 20 19.7 9.3 35.5 0.311 — — —— — 27.6 0.337 18.0 42.0 102.2 Comparative 0.5 55.1 15.9 198.0 0.181 0.558.1 22.1 177.0  0.109 26.6 0.338 17.4 40.4 100.0 Example 1

As shown in Table 1, the β-sialon fluorescent materials of Examples 1 to6 in which in the first or second grinding step, the calcined product orheat-treated product was strongly ground so as to have a specificsurface area of 0.2 m²/g or more, followed by achieving the heattreatment step exhibited a higher light emission intensity than theβ-sialon fluorescent material of Comparative Example 1 in which thestrong grinding was not performed.

As shown in Table 1, in Examples 1 to 5, the β-sialon fluorescentmaterials are obtained by repeating the grinding step and the heattreatment step two times in this step order. The thus obtained β-sialonfluorescent materials of Examples 1 to 5 exhibited a higher relativelight emission intensity than the β-sialon fluorescent material ofExample 6 in which the grinding step and the heat treatment step wereperformed only one time in this step order.

In particular, as shown in Table 1, in Examples 2 to 5, the grindingstep and the heat treatment step are repeated in this order two times,and in at least one grinding step, the strong grinding is performed suchthat the specific surface area of the ground product is 0.35 m²/g ormore. The thus obtained β-sialon fluorescent materials of Examples 2 to5 exhibited higher light emission intensities than those of Examples 1and 6. Furthermore, as shown in Table 1, in Examples 4 and 5, in atleast one grinding step, the strong grinding is performed such that thespecific surface area of the ground product is 0.37 m²/g or more. Thethus obtained β-sialon fluorescent materials of Examples 4 and 5exhibited still higher light emission intensities than those of theother Examples.

In addition, as shown in FIG. 1, the light emission spectrum of thefluorescent material of Example 1 and the light emission spectrum of thefluorescent material of Comparative Example 1 are substantially the sameas each other in the light emission peak wavelength and the shape of thelight emission spectrum; however, the fluorescent material of Example 1is higher in the light emission peak than the fluorescent material ofComparative Example 1, and thus, it is noted that the light emissionintensity of the fluorescent material of Example 1 becomes high.

As shown in Table 1, the ground products, which were strongly ground inthe first grinding step and the second grinding step so as to have aspecific surface area of 0.20 m²/g or more, contain relatively largeparticles together with small particles as shown in the SEM photographsof FIG. 2A and FIG. 2B. In the β-sialon fluorescent material of Example1, in the heat treatment step after the grinding step, the reactionbetween the small particle and the large particle is more advanced tocause the rearrangement of crystal, and not only the activating elementis readily incorporated into the rearranged crystal, but also theheat-treated product can be grown to a desired size. Thus, it isestimated that the light emission intensity is enhanced.

On the other hand, as shown in the SEM photographs of FIG. 3A, FIG. 3Band FIG. 3C in Comparative Example 1 in which the strong grinding wasnot performed in the first grinding step and the second grinding step,the presence of agglomerates was confirmed, and the amount of smallparticles was small as compared with the ground products of Example 1 asshown in the SEM photographs of FIG. 2A, FIG. 2B and FIG. 2C.

As shown in Comparative Example 1 of Table 1, in the case where thestrong grinding of the calcined product or heat-treated product was notperformed, and the crushing or coarse grinding was performed in thefirst grinding step and the second grinding step such that the specificsurface area was smaller than 0.20 m²/g, the improvement in the lightemission intensity as in the Examples could not be confirmed.

As shown in Table 1, the particle diameter D10 at which the volumecumulative frequency reaches 10% from the small diameter side in theparticle size distribution was 3 μm or more and 10.5 μm or less withrespect to the first ground product or the second ground product in eachof the Examples. On the other hand, as shown in Table 1, the D10 ofComparative Example 1 was larger than 12 μm with respect to the firstground product and the second ground product.

As shown in Table 1, the particle diameter D90 at which the volumecumulative frequency reaches 90% from the small diameter side in theparticle size distribution was 20 μm or more and 40 μm or less withrespect to the first ground product or the second ground product in eachof the Examples. On the other hand, as shown in Table 1, the D90 ofComparative Example 1 was at least 3 times larger than 50 μm withrespect to the first ground product and the second ground product.

The standard deviation (σ) in the particle size distribution of theβ-sialon fluorescent material was 0.4 or less in each of the Examples,and a β-sialon fluorescent material having a uniform particle diameterwas obtained.

The β-sialon fluorescent material produced by the methods as disclosedherein is high in the light emission intensity, and by using thisβ-sialon fluorescent material, a light emitting device having a highlight emission intensity can be configured.

Although the present disclosure has been described with reference toseveral exemplary embodiments, it shall be understood that the wordsthat have been used are words of description and illustration, ratherthan words of limitation. Changes may be made within the purview of theappended claims, as presently stated and as amended, without departingfrom the scope and spirit of the disclosure in its aspects. Although thedisclosure has been described with reference to particular examples,means, and embodiments, the disclosure may be not intended to be limitedto the particulars disclosed; rather the disclosure extends to allfunctionally equivalent structures, methods, and uses such as are withinthe scope of the appended claims.

One or more examples or embodiments of the disclosure may be referred toherein, individually and/or collectively, by the term “disclosure”merely for convenience and without intending to voluntarily limit thescope of this application to any particular disclosure or inventiveconcept. Moreover, although specific examples and embodiments have beenillustrated and described herein, it should be appreciated that anysubsequent arrangement designed to achieve the same or similar purposemay be substituted for the specific examples or embodiments shown. Thisdisclosure may be intended to cover any and all subsequent adaptationsor variations of various examples and embodiments. Combinations of theabove examples and embodiments, and other examples and embodiments notspecifically described herein, will be apparent to those of skill in theart upon reviewing the description.

In addition, in the foregoing Detailed Description, various features maybe grouped together or described in a single embodiment for the purposeof streamlining the disclosure. This disclosure may be not to beinterpreted as reflecting an intention that the claimed embodimentsrequire more features than are expressly recited in each claim. Rather,as the following claims reflect, inventive subject matter may bedirected to less than all of the features of any of the disclosedembodiments. Thus, the following claims are incorporated into theDetailed Description, with each claim standing on its own as definingseparately claimed subject matter.

The above disclosed subject matter shall be considered illustrative, andnot restrictive, and the appended claims are intended to cover all suchmodifications, enhancements, and other embodiments which fall within thetrue spirit and scope of the present disclosure. Thus, to the maximumextent allowed by law, the scope of the present disclosure may bedetermined by the broadest permissible interpretation of the followingclaims and their equivalents, and shall not be restricted or limited bythe foregoing detailed description.

What is claimed is:
 1. A method of producing a β-sialon fluorescentmaterial, comprising: preparing a calcined product having a compositionof β-sialon containing an activating element by calcining a raw materialmixture containing a first compound containing an activating element;grinding the calcined product together with a second compound containingan activating element in the absence of another raw material for makingβ-sialon to obtain a ground product, wherein the ground product does notcontain a raw material for making β-sialon other than the secondcompound containing the activating element; and heat-treating the groundproduct to obtain a heat-treated product, wherein the first compoundcontaining the activating element and the second compound containing theactivating element do not have a composition of a β-sialon containing anactivating element.
 2. The method of producing a β-sialon fluorescentmaterial according to claim 1, wherein a molar ratio of the activatingelement contained in the second compound containing the activatingelement is smaller than a ratio of the activating element in the firstcompound containing the activating element in the raw material mixture.3. The method of producing a β-sialon fluorescent material according toclaim 1, wherein a particle diameter D10, at which a volume cumulativefrequency reaches 10% from a small diameter side in a particle sizedistribution, of the ground product is 1 μm or more and 12 μm or less.4. The method of producing a β-sialon fluorescent material according toclaim 1, wherein a particle diameter D90, at which a volume cumulativefrequency reaches 90% from a small diameter side in a particle sizedistribution, of the ground product is 15 μm or more and 50 μm or less.5. The method of producing a β-sialon fluorescent material according toclaim 1, wherein the heat-treating is performed in an inert gasatmosphere.
 6. The method of producing a β-sialon fluorescent materialaccording to claim 1, wherein the heat-treating is performed at atemperature in a range of 1,850° C. or higher and 2,100° C. or lower. 7.The method of producing a β-sialon fluorescent material according toclaim 1, wherein the activating element is at least one element selectedfrom the group consisting of Eu, Ce, Tb, Yb, Sm, and Dy, the firstcompound containing the activating element and the second compoundcontaining the activating element are at least one selected from thegroup consisting of an oxide, a hydroxide, a nitride, an oxynitride, afluoride and a chloride, and when a molar ratio of the activatingelement contained in the resulting β-sialon fluorescent material isdefined as 1, a molar ratio of the activating element in the firstcompound containing the activating element is 0.55 or more, a molarratio of the activating element in the second compound containing theactivating element is 0.45 or less.
 8. The method of producing aβ-sialon fluorescent material according to claim 1, further comprisingannealing the heat-treated product in a noble gas atmosphere at atemperature lower than a heat treatment temperature in the heat-treatingstep, to obtain an annealed product.
 9. The method of producing aβ-sialon fluorescent material according to claim 8, wherein in theannealing step, the heat-treated product is annealed together with acompound containing an activating element.
 10. The method of producing aβ-sialon fluorescent material according to claim 8, further comprisingbringing the heat-treated product or the annealed product into contactwith an acidic solution or a basic substance, wherein the basicsubstance is at least one selected from the group consisting of LiOH,NaOH, KOH, RbOH, CsOH and NH₃.
 11. A method of producing a β-sialonfluorescent material, comprising: preparing a calcined product having acomposition of β-sialon containing an activating element by calcining araw material mixture containing a first compound containing anactivating element; grinding the calcined product together with a secondcompound containing an activating element in the absence of a rawmaterial for making β-sialon other than the second compound containingthe activating element to obtain a ground product, wherein the groundproduct does not contain a raw material for making β-sialon other thanthe second compound containing the activating element; and heat-treatingthe ground product to obtain a heat-treated product, wherein thegrinding step and the heat-treating step are repeated two times or morein this order, and in at least one grinding step, an average particlediameter of the ground product is 40 μm or less, wherein the firstcompound containing the activating element and the second compoundcontaining the activating element do not have a composition of aβ-sialon containing an activating element.
 12. The method of producing aβ-sialon fluorescent material according to claim 11, wherein a molarratio of the activating element contained in the second compoundcontaining the activating element is smaller than a molar ratio of theactivating element in the first compound containing the activatingelement in the raw material mixture.
 13. The method of producing aβ-sialon fluorescent material according to claim 11, wherein a particlediameter D10, at which a volume cumulative frequency reaches 10% from asmall diameter side in a particle size distribution, of the groundproduct is 1 μm or more and 12 μm or less.
 14. The method of producing aβ-sialon fluorescent material according to claim 11, wherein a particlediameter D90, at which a volume cumulative frequency reaches 90% from asmall diameter side in a particle size distribution, of the groundproduct is 15 μm or more and 50 μm or less.
 15. The method of producinga β-sialon fluorescent material according to claim 11, wherein theheat-treating is performed in an inert gas atmosphere.
 16. The method ofproducing a β-sialon fluorescent material according to claim 1, whereinthe heat-treating is performed at a temperature in a range of 1,850° C.or higher and 2,100° C. or lower.
 17. The method of producing a β-sialonfluorescent material according to claim 11, wherein the activatingelement is at least one element selected from the group consisting ofEu, Ce, Tb, Yb, Sm, and Dy, the first compound containing the activatingelement and the second compound containing the activating element are atleast one selected from the group consisting of an oxide, a hydroxide, anitride, an oxynitride, a fluoride and a chloride, and when a molarratio of the activating element contained in the resulting β-sialonfluorescent material is defined as 1, a molar ratio of the activatingelement in the first compound containing the activating element is 0.55or more, a molar ratio of the activating element in the second compoundcontaining the activating element is 0.45 or less.
 18. The method ofproducing a β-sialon fluorescent material according to claim 11, furthercomprising annealing the heat-treated product in a noble gas atmosphereat a temperature lower than a heat treatment temperature in theheat-treating step, to obtain an annealed product.
 19. The method ofproducing a β-sialon fluorescent material according to claim 18, whereinin the annealing step, the heat-treated product is annealed togetherwith a compound containing an activating element.
 20. The method ofproducing a β-sialon fluorescent material according to claim 18, furthercomprising bringing the heat-treated product or the annealed productinto contact with an acidic solution or a basic substance, wherein thebasic substance is at least one selected from the group consisting ofLiOH, NaOH, KOH, RbOH, CsOH and NH₃.